CN101583423A - Engine exhaust catalysts containing palladium-gold - Google Patents

Engine exhaust catalysts containing palladium-gold Download PDF

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Publication number
CN101583423A
CN101583423A CNA2007800501179A CN200780050117A CN101583423A CN 101583423 A CN101583423 A CN 101583423A CN A2007800501179 A CNA2007800501179 A CN A2007800501179A CN 200780050117 A CN200780050117 A CN 200780050117A CN 101583423 A CN101583423 A CN 101583423A
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China
Prior art keywords
catalyst
coating
emission control
single piece
base material
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CNA2007800501179A
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CN101583423B (en
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凯尔·L·福基达拉
蒂莫西·J·楚克斯
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Nanostellar Inc
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Nanostellar Inc
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Priority claimed from US11/624,128 external-priority patent/US7709414B2/en
Priority claimed from US11/942,710 external-priority patent/US7534738B2/en
Application filed by Nanostellar Inc filed Critical Nanostellar Inc
Priority claimed from PCT/US2007/088085 external-priority patent/WO2008088649A1/en
Publication of CN101583423A publication Critical patent/CN101583423A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/644—Arsenic, antimony or bismuth
    • B01J23/6447—Bismuth
    • B01J35/19—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F01N13/0093—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are of the same type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
    • F01N3/106—Auxiliary oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/106—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B01J35/40—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0248—Coatings comprising impregnated particles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2430/00—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
    • F01N2430/08—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by modifying ignition or injection timing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
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    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/10—Carbon or carbon oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/0231—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using special exhaust apparatus upstream of the filter for producing nitrogen dioxide, e.g. for continuous filter regeneration systems [CRT]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/025—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using fuel burner or by adding fuel to exhaust
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    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Abstract

An emission control catalyst that exhibits improved CO and HC reduction performance includes a supported platinum-based catalyst, and a supported palladium-gold catalyst. The two catalysts are coated onto different layers, zones, or monoliths of the substrate for the emission control catalyst such that the platinum-based catalyst encounters the exhaust stream before the palladium-gold catalyst. Zeolite may be added to the emission control catalyst as a hydrocarbon absorbing component to boost the oxidation activity of the palladium-gold catalyst.

Description

The engine exhaust catalysts that contains palladium-Jin
Technical field
Embodiments of the present invention relate generally to contain the supported catalyst of noble metal, relate more specifically to contain the engine exhaust catalysts and the manufacture method thereof of palladium and gold.
Background technology
If do not use catalyst, just can't produce many industrial products such as fuel, lubricant, polymer, fiber, medicine and other chemicals.For reducing pollutant, particularly reduce the pollutant that produces by automobile in the neutralization of production of energy process, catalyst also is essential.Many industrial catalysts are made up of the high surface area support material that is dispersed with reactive metal nano particle (being the metallic particles of nano-scale) on it.This carrier material is the ceramic-like materials of inertia normally, and its surface area magnitude is in hundreds of meters squared per gram.So high specific area needs complicated internal holes system usually.Metal nanoparticle is deposited on the carrier and is dispersed in the whole internal holes system, and its size is generally the 1-100 nanometer.
The method for preparing supported catalyst is of long duration.For example, a kind of method for preparing platinum catalyst comprises making such as the carrier material of aluminium oxide and contacts with metal salt solution such as the chloroplatinic acid aqueous solution.In this process, the hole of metal salt solution " dipping " or filling carrier.After the dipping, will contain the carrier drying of metal salt solution, and make slaine in the hole, precipitate.To contain the carrier calcining (usually in air) of the slaine of precipitation then, and be exposed to reducing gas environment (for example, hydrogen or carbon monoxide) with further reduction formation metallic particles.The another kind of method for preparing supported catalyst comprises the step that makes carrier material and the step and the use appropriate reductant of metal salt solution the metal ion in-situ reducing be become metallic particles.
Supported catalyst is very useful for removing from vehicle exhaust the pollutant.Vehicle exhaust comprises noxious pollutant, and for example carbon monoxide (CO), unburned hydrocarbon (HC) and nitrogen oxide (NOx), these pollutants cause the puzzlement whole world each metropolitan " fogging effect ".Used the catalytic converter and the particulate filter that contain supported catalyst to come from vehicle exhaust, to remove these noxious pollutants.Although since using catalytic converter and particulate filter, the pollution that vehicle exhaust caused descends year by year, but it is because more and more stricter to the requirement of control vehicle emission, and motor vehicle manufacturers attempts to use more a spot of noble metal for the totle drilling cost that reduces emission control in supported catalyst, therefore studying the supported catalyst that improves always.
The prior art instruction uses the supported catalyst that contains palladium and gold as good partial oxidation catalyst.And the gas phase that is reflected at that this catalyst also is used in a large number by ethene, acetate and oxygen is produced vinyl acetate (for example seeing U.S. Pat 6022823).Control is used for vehicle emission, and US 6763309 infers that palladium-Jin may be a kind of good candidate's bimetallic catalyst that is used to improve the NO decomposition rate.Yet the disclosure content is based on Mathematical Modeling, and can not obtain the experimental data support.Do not instruct palladium-Jin system can handle the vehicle emission that comprises CO and HC in this patent yet.
Summary of the invention
The invention provides the emission control catalyst and the manufacture method thereof that are used to handle the emission that comprises CO and HC.Engine can be vehicle motor, industrial engine, or generally speaking, the engine of any kind of burning hydrocarbon.
Emission control catalyst according to the embodiment of the present invention comprises loaded platinum based catalyst and loaded palladium-gold catalyst.These two kinds of catalyst are applied on different layers, zone or the single piece of material of base material of emission control catalyst, contact so that platinum based catalyst flowed with exhaust before palladium-gold catalyst.Zeolite can be used as the hydrocarbon absorbent components and adds emission control catalyst, to improve the oxidation activity of palladium-gold catalyst.
The inventor found through experiments, and the HC material that exists in the exhaust can suppress the oxidation activity of emission control catalyst, and by addressing this problem, the inventor has realized using the supported catalyst that comprises palladium and gold to control catalyst as emission.According to the present invention, by exhaust was exposed to platinum based catalyst before being exposed to palladium-gold catalyst, and/or by adding the hydrocarbon absorbing material, the overall catalytic activity that can improve the oxidation activity of palladium-gold catalyst and emission can be controlled catalyst is brought up to level of significance, comes to reduce fully the HC depression effect thus.The inventor confirms by vehicle performance test, and is good equally in the CO that reduces vehicle and the performance aspect the HC emission and platinum-palladium catalyst according to the emission control catalyst of embodiment of the present invention.
Description of drawings
In order at length to understand These characteristics of the present invention, reference implementation mode (some embodiment is shown in accompanying drawing) is more specifically described the present invention.But should be noted that accompanying drawing only shows exemplary embodiment of the present invention, therefore should not think that accompanying drawing limits the scope of the invention, the present invention can comprise other same useful embodiment.
Figure 1A-1D is the schematic diagram that can use the different engine exhaust systems of embodiments of the present invention;
Fig. 2 is the diagram of catalytic converter, and the part of dissecing wherein shows the base material that the emission that is coated with on it is according to the embodiment of the present invention controlled catalyst;
Fig. 3 A-3D shows the different structure of the base material that is used for emission control catalyst;
Fig. 4 shows the flow chart for preparing the step of emission control catalyst according to one embodiment of the present invention;
Fig. 5 shows the flow chart for preparing the step of emission control catalyst according to another embodiment of the invention.
The specific embodiment
Below with reference to embodiments of the present invention.But should be appreciated that and the invention is not restricted to these specific embodiment.On the contrary, will be appreciated that any combination of following feature and key element (no matter whether relating to different embodiments) all can be implemented the present invention.In addition, in various embodiments, the invention provides a plurality of advantages that are better than prior art.Yet though embodiments of the present invention can have the advantage that is better than other possible solution and/or prior art, whether concrete advantage obtains not limit the present invention by given embodiment.Therefore, unless clearly put down in writing in the claims, following aspect, feature, embodiment and advantage only are exemplary, and should not be counted as the technical characterictic of claims.Similarly, unless clearly put down in writing in the claims, alleged " the present invention " should not be interpreted as the summary of subject matter disclosed herein, and should not be considered to constitute the technical characterictic of claims.
Figure 1A-1D is the schematic diagram that can use the different engine exhaust systems of embodiments of the present invention.The combustion process that takes place in the engine 102 produces noxious pollutant, CO, various hydrocarbon, particle and nitrogen oxide (NOx) during for example the exhaust of discharging by the tail pipe 108 of gas extraction system is flowed.
In the gas extraction system of Figure 1A, the exhaust stream that comes out from engine 102 passes catalytic converter 104, is discharged in the atmosphere (environment) by tail pipe 108 then.Catalytic converter 104 comprises the supported catalyst of the processing engine 102 exhausts stream that is coated on the monolithic substrate.Handle exhaust stream by the various catalytic reactions that occur in catalytic converter 104 inside.These reactions comprise CO are oxidized to CO 2, the burning of hydrocarbon and NO be to NO 2Conversion.
In the gas extraction system of Figure 1B, the exhaust stream of engine 102 passes catalytic converter 104 and particulate filter 106, is discharged in the atmosphere by tail pipe 108 then.Identical in the mode of operation of catalytic converter 104 and the gas extraction system of Figure 1A.Particulate filter 106 captures the particulate matter in the exhaust stream, for example flue dust, liquid hydrocarbon (being generally the particle of liquid form).In a kind of optional structure, particulate filter 106 comprises the coating supported catalyst that is used for oxidation NO and/or the burning of promotion particulate matter thereon.
In the gas extraction system of Fig. 1 C, the exhaust stream of engine 102 passes catalytic converter 104, prefilter catalyst 105 and particulate filter 106, is discharged in the atmosphere by tail pipe 108 then.Identical in the mode of operation of catalytic converter 104 and the gas extraction system of Figure 1A.The prefilter catalyst comprises monolithic substrate and the supported catalyst that is used for oxidation NO that is coated on the monolithic substrate.Particulate filter 106 captures the particulate matter in the exhaust stream, for example flue dust, liquid hydrocarbon (being generally the particle of liquid form).
In the gas extraction system of Fig. 1 D, the exhaust stream of engine 102 passes catalytic converter 104, particulate filter 106, SCR (SCR) unit 107 and ammonia and leaks catalyst 110, is discharged in the atmosphere by tail pipe 108 then.Identical in the mode of operation of catalytic converter 104 and the gas extraction system of Figure 1A.Particulate filter 106 captures the particulate matter in the exhaust stream, for example flue dust, liquid hydrocarbon (being generally the particle of liquid form).In a kind of optional structure, particulate filter 106 comprises the coating supported catalyst that is used for oxidation NO and/or the burning of promotion particulate matter thereon.SCR unit 107 is provided for the NOx material is reduced into N 2SCR unit 107 can be based on ammonia/urea or based on hydrocarbon.Ammonia leakage catalyst 110 is provided for reducing the amount by the emission intensity thing of tail pipe 108.Another kind of structure is that SCR unit 107 is arranged on before the particulate filter 106.
Other configuration mode of gas extraction system is included in and SCR unit 107 and ammonia are set in the gas extraction system of Figure 1A or 1C leak catalyst 110 and in the gas extraction system of Figure 1A, 1B or 1C SCR unit 107 only is set and ammonia is not set leaks catalyst 110.
Become trapped in along with particle in the particulate filter in the gas extraction system of Figure 1B, 1C or 1D, the deterioration of efficiency of this particulate filter need be regenerated to it.The regeneration of particulate filter both can be passive also can be initiatively.Passive regeneration is at NO 2Existence take place down automatically.Therefore, when containing NO 2Exhaust stream when passing particulate filter, passive regeneration takes place.In regenerative process, the oxidized and NO of particle 2Be converted into NO.Generally speaking, higher NO 2Amount can be improved regenerability, so this process is commonly called NO 2Assisted oxidation.Yet, NO 2Do not expect too much, because excessive N O 2Be released in the atmosphere, and NO 2Be considered to the pollutant more harmful than NO.In combustion process, by the NO oxidation in the catalytic converter 104, in the prefilter catalyst 105 the NO oxidation and/or have the NO oxidation of the particulate filter 106 of catalyst, can in engine, be formed for the NO that regenerates 2
Initiative regeneration carries out by heated particle filter 106 and with particulate oxidation.Under higher temperature, NO 2Booster action to particulate oxidation reduces.The heating of particulate filter 106 can be undertaken by variety of way known in the art.A kind of mode is to adopt fuel burner that particulate filter 106 is heated to the particle burning temperature.Another kind of mode is to adjust the temperature that engine output improves exhaust stream when the particulate filter load reaches predeterminated level.
The invention provides the catalyst of the catalytic converter 104 that is used for shown in Figure 1A-1D, perhaps usually as the catalyst in any vehicle emission control system, comprise that diesel oxidation catalyst, diesel fuel filter catalyst, ammonia leak catalyst, SCR catalyst or as the component of three-way catalyst.The present invention also provides a kind of vehicle emission control system that comprises emission control catalyst, and those shown in Figure 1A-1D for example, this catalyst comprise single piece of material and are coated in supported catalyst on the single piece of material.
Fig. 2 is the diagram of catalytic converter, and the part of dissecing wherein shows the base material 210 that is coated with supported metal catalyst on it.The enlarged drawing of base material 210 shows that base material 210 has honeycomb, and this structure comprises a plurality of passages, contain the coating (washcoat) of supported metal catalyst thus flowing into described passage with the slurries form forms coating 220 on base material 210.
Fig. 3 A-3D shows different embodiment of the present invention.In the embodiment of Fig. 3 A, coating 220 comprises two dope layers 221,223 that are positioned at base material 210 tops.Dope layer 221 is the bottoms that are located immediately at base material 210 tops, and it comprises palladium and the golden metallic particles (being also referred to as " palladium-Jin metallic particles ") that contains tight contact.Dope layer 223 is the top layers that directly contact with exhaust stream, its comprise a platiniferous or with the another kind of metallics metallic particles (being also referred to as " platinum metal particle ") of the tight platinum that contacts of palladium for example.According to they positions with respect to exhaust stream, dope layer 223 contacted with exhaust stream before dope layer 221.
In the embodiment of Fig. 3 B, coating 220 comprises the dope layer 221,222,223 that is positioned at base material 210 tops.Dope layer 221 is the bottoms that are located immediately at base material 210 tops, and it comprises palladium-Jin metallic particles.Dope layer 223 is the top layers that directly contact with exhaust stream, and it comprises the platinum metal particle.Dope layer 222 is intermediate layer or the cushions between dope layer 221 and 223.The intermediate layer is provided for making the interaction minimum between Pt component and Pd-Au component.The intermediate layer can be the palladium particle that blank carrier maybe can comprise zeolite, rare earth oxide, inorganic oxide and/or support.According to they positions with respect to exhaust stream, dope layer 223 contacted with exhaust stream before dope layer 221,222, and dope layer 222 contacted with exhaust stream before dope layer 221.
In the embodiment of Fig. 3 C, base material 210 is the single single piece of material with two coated areas 210A, 210B.The coating that comprises the platinum metal particle is applied on the first district 210A, and comprises that the coating of palladium-Jin metallic particles is applied on the second district 210B.
In the embodiment of Fig. 3 D, base material 210 comprises first and second single piece of material 231,232, and these two single piece of material are the single piece of material of separating physically.The coating that comprises the platinum metal particle is applied on first single piece of material 231, comprises that the coating of palladium-Jin metallic particles is applied on second single piece of material 232.
Above-mentioned embodiment includes the palladium-gold catalyst with the platinum based catalyst combination.Palladium in the palladium-gold catalyst is about 0.05 with the weight ratio of gold: 1-20: 1, preferred about 0.5: 1-2: 1.Palladium-gold catalyst can promote with bismuth or other known promoter.The platinum catalyst that platinum based catalyst can be platinum catalyst, platinum-palladium catalyst, promote with bismuth or other known promoter, or other platinum based catalyst (for example, Pt-Rh, Pt-Ir, Pt-Ru, Pt-Au, Pt-Ag, Pt-Rh-Ir, Pt-Ir-Au etc.).Preferred embodiment adopt platinum-palladium catalyst as platinum based catalyst.The platinum in this catalyst and the weight ratio of palladium are about 0.05: 1-20: 1, preferred about 2: 1-4: 1.
In addition, the position of platinum based catalyst can make it contact exhaust stream before palladium-gold catalyst.The inventor finds, in this way platinum based catalyst is located with respect to palladium-gold catalyst, HC can be reduced to the level that is enough to improve overall catalytic performance to the depression effect of the oxidation activity of palladium-gold catalyst.In the embodiment of Fig. 3 A and 3B, platinum based catalyst is included in the top layer 223, and palladium-gold catalyst is included in the bottom 221.In the embodiment of Fig. 3 C, platinum based catalyst is included among the first district 210A, and palladium-gold catalyst is included among the second district 210B.In the embodiment of Fig. 3 D, platinum based catalyst is included in first single piece of material 231, and palladium-gold catalyst is included in second single piece of material 232.
In other embodiment of the present invention, in emission control catalyst, add the hydrocarbon absorbing material.Preferably, the hydrocarbon absorbing material is added in the emission control catalyst, so that it contacted with exhaust stream before palladium-gold catalyst.The inventor finds, in this way the hydrocarbon absorbing material is located with respect to palladium-gold catalyst, HC can be reduced to the level that is enough to improve overall catalytic performance to the depression effect of the oxidation activity of palladium-gold catalyst.In the structure shown in Fig. 3 A, the hydrocarbon absorbing material can be included in the top layer 223.In the structure shown in Fig. 3 B, the hydrocarbon absorbing material can be included in intermediate layer 222 or the top layer 223.In the structure shown in Fig. 3 C, the hydrocarbon absorbing material can be included among the first district 210A.In the structure shown in Fig. 3 D, the hydrocarbon absorbing material can be included in the single piece of material 231 of front.In the following embodiments, the hydrocarbon absorbing material is a zeolite.Zeolite can be the mixture of β zeolite, ZSM-5 zeolite and any weight ratio of these two kinds of zeolites (containing or do not contain the zeolite of other type).
In other embodiment of the present invention, any dope layer or district or single piece of material can comprise rare earth oxide, for example cerium (IV) oxide (CeO 2) and cerium oxide-zirconia (CeO 2-ZrO 2).
Fig. 4 shows the flow chart that uses the step of base material 210 preparation emission control catalyst according to one embodiment of the present invention.In step 410, prepare first supported catalyst with the method for describing among known method or the following embodiment, for example loaded palladium-gold catalyst.In step 412, prepare second supported catalyst with the method for describing among known method or the following embodiment, for example loaded platinum based catalyst.In step 414, provide monolithic substrate, base material 210 for example shown in Figure 2 (or monolithic substrate shown in Fig. 3 D 231,232).Exemplary monolithic substrate comprises those base materials based on pottery (for example cordierite), metal or carborundum.In step 416, first supported catalyst of powder type is mixed in solvent to form the coating slurries, then the coating slurries are applied as the bottom of base material 210 be coated to the back zone of base material 210 or the single piece of material of back on.In step 418, second supported catalyst of powder type is mixed in solvent to form the coating slurries, then the coating slurries are applied as the top layer of base material 210 be coated to the proparea of base material 210 or the single piece of material of front on.Alternatively, in step 418, apply before the coating slurries, zeolite or the zeolite mixture that comprises one or more kinds in the zeolite of β zeolite, ZSM-5 zeolite and other type added in the carrier pulp.
Fig. 5 shows according to the flow chart of another embodiment of the invention with the step of base material 210 preparation emission control catalyst.In step 510, prepare first supported catalyst with the method for describing among known method or the following embodiment, for example loaded palladium-gold catalyst.In step 512, prepare second supported catalyst with the method for describing among known method or the following embodiment, for example loaded platinum based catalyst.In step 514, provide monolithic substrate, base material 210 for example shown in Figure 2.Exemplary monolithic substrate comprises those base materials based on pottery (for example cordierite), metal or carborundum.In step 516, first supported catalyst of powder type is mixed in solvent to form the coating slurries, then the coating slurries are applied bottom as base material 210.In step 517, zeolite or zeolite mixture are added in the solvent forming the coating slurries, and apply the intermediate layer of these coating slurries as base material 210.In step 518, second supported catalyst of powder type is mixed in solvent to form the coating slurries, then the coating slurries are applied top layer as base material 210.
The vehicle performance data of various embodiments of the present invention are listed in table 1-4.
Table 1
Embodiment Bottom The intermediate layer Top layer CO emission (g/km) HC emission (g/km)
1 PtPd (2.8%: 1.4% weight ratio), 57.5g/ft 3 The β zeolite, 0.5g/in 3 PtPd (2.8%: 1.4% weight ratio), 57.5g/ft 3 0.366 0.079
2 PtPd (2.8%: 1.4% weight ratio), 57.5g/ft 3 β zeolite and ZSM-5 zeolite (1: 1 weight ratio) PtPd (2.8%: 1.4% weight ratio), 57.5 g/ft 3 0.332 0.066
3 test A PdAu (1.7%: 2.0% weight ratio), 65g/ft 3 β zeolite and ZSM-5 zeolite (1: 1 weight ratio) PtPd (3.0%: 0.75% weight ratio), 65.0g/ft 3 0.296 0.049
3 test bs PdAu (1.7%: 2.0% weight ratio), 65g/ft 3 β zeolite and ZSM-5 zeolite (1: 1 weight ratio) PtPd (3.0%: 0.75% weight ratio), 65.0g/ft 3 0.296 0.057
Table 2
Embodiment Preceding piece Back piece CO emission (g/km) HC emission (g/km)
4 PtPd (2.0%: 1.0% weight ratio), 120g/ft 3 PtPd (2.0%: 1.0% weight ratio), 120g/ft 3 0.143 0.0539
5 PtPd (2.0%: 1.0% weight ratio), 120g/ft 3 PdAu (1.7%: 2.0% weight ratio), 175g/ft 3 0.146 0.0474
6 PtPd (3.0%: 0.75% weight ratio), 130g/ft 3 PdAu (1.7%: 2.0% weight ratio), 130g/ft 3 0.121 0.0505
7 PtPd (3.0%: 0.75% weight ratio), 150g/ft 3 PdAu (1.7%: 2.0% weight ratio), 130g/ft 3 0.123 0.0385
Table 3
Embodiment Preceding piece Back piece CO emission (g/km)
8 PtPd (2.8%: 1.4% or 2: 1 weight ratios), 170g/ft 3 Blank 0.171
9 PtPd (2.8%: 1.4% or 2: 1 weight ratios), 170g/ft 3 PdAu (1.7%: 2.0% or 0.85: 1.0 weight ratio), 146g/ft 3 0.065
10 PtBi (3.0%: 2.0% or 1.5: 1 weight ratios), 120g/ft 3 PdAu (1.7%: 2.0% or 0.85: 1.0 weight ratio), 146g/ft 3 0.078
Table 4
Embodiment Bottom The intermediate layer Top layer CO emission (g/km)
11 PdAu (1.7%: 2.0% or 0.85: 1.0 weight ratio), 73g/ft 3 Pd (3.0% weight ratio) is supported on the rare earth oxide 30g/ft 3 PtPd (2.8%: 1.4% or 2: 1 weight ratios), 85g/ft 3 0.137
For the data shown in the table 1-4, the packet (bag data) that the European MVEG test of use standard obtains is measured CO and the HC emission that light diesel car (model in 2005) tail pipe is discharged.Data in table 1 and the table 2 show the vehicle testing performance of seven kinds of catalyst, these catalyst have identical noble metal cost (assumed cost with 4: 1: 2 Pt: Pd: Au is a benchmark), and launched machine aging 20 hours (by the double mode circulation of using fuel to spray, so that reaction bed temperature is about 650 ℃).Data in table 3 and the table 4 show the fresh CO oxidation vehicle performance of four kinds of catalyst, and these catalyst have identical noble metal cost (assumed cost with 4: 1: 2 Pt: Pd: Au is a benchmark).The embodiment of table 1 is in low engine discharge temperature (engine outtemperature) (about 150-300 ℃) test down, and the embodiment of table 2 is in high-engine discharge temperature (about 200-350 ℃) test down.It is that 5.66 inches and length are on 2.5 inches the cordierite substrates that embodiment 1-3 and 11 catalyst are applied to diameter.It is that 5.66 inches and length are on 1.25 inches a pair of cordierite substrates that the catalyst of embodiment 4-10 is applied to diameter.
Table 1 shows the data of the emission control catalyst (seeing Fig. 3 B) with three-decker.Embodiment 1 representative is as the emission control catalyst of reference, comprises the metallic particles (being also referred to as " platinum-palladium metal particle ") that contains tight platinum that contacts and palladium in its bottom and the top layer, and the weight ratio of platinum and palladium is 2.8%: 1.4%.The intermediate layer comprises the β zeolite.Embodiment 2 represents another kind of emission control catalyst as reference, and its compositions is identical with embodiment 1, is that to comprise weight ratio be 1: 1 the β zeolite and the zeolite mixture of ZSM-5 zeolite in the intermediate layer.Embodiment 3 representatives emission control catalyst according to the embodiment of the present invention, its weight ratio that comprises in bottom is palladium-Jin metallic particles of 1.7%: 2.0% and comprises that in top layer weight ratio is platinum-palladium metal particle of 3.0%: 0.75%.It is 1: 1 the β zeolite and the zeolite mixture of ZSM-5 zeolite that the intermediate layer comprises weight ratio.With respect to the reference emission control catalyst of embodiment 1 and 2, find that the emission control catalyst of embodiment 3 all reduces to some extent on HC and CO emission.
Table 2 shows the emission control catalyst (seeing Fig. 3 D) with two pieces (dual-brick) structure.Embodiment 4 representatives are as the emission control catalyst of reference, and it comprises that weight ratio is platinum-palladium metal particle of 2.0%: 1.0% in preceding (frontbrick) and back piece (rear brick).Embodiment 5,6 and 7 representatives emission control catalyst according to the embodiment of the present invention, every kind of catalyst comprises palladium-Jin metallic particles.Embodiment 5 comprises that in preceding weight ratio is platinum-palladium metal particle of 2.0%: 1.0% and comprises that weight ratio is palladium-Jin metallic particles of 1.7%: 2.0% in the piece of back.Embodiment 6 comprises that in preceding weight ratio is platinum-palladium metal particle of 4.0%: 1.0% and comprises that weight ratio is palladium-Jin metallic particles of 1.7%: 2.0% in the piece of back.Embodiment 7 comprises that in preceding weight ratio is platinum-palladium metal particle of 2.0%: 1.0% and comprises that weight ratio is palladium-Jin metallic particles of 1.7%: 2.0% in the piece of back.Among the embodiment 7 two use the coating slurries that added cerium oxide-zirconia (all the other are noble metal and alumina powder) of about 28%.With respect to the reference emission control catalyst of embodiment 4, find the HC emission minimizing of the emission control catalyst among the embodiment 5,6 and 7 and have similar or better CO oxidation susceptibility.
Data in the table 3 and 4 show, in other embodiment of the present invention, for when using a plurality of base materials (embodiment 9 and 10) or use the catalyst based and Pd-Au catalyst of multilayer Pt on the single base material, be enhanced without the performance of aging catalyst with the catalyst based and Pd-Au catalyst of Pt.Should be noted that when the Pt-Pd of embodiment 9 piece and blank block but not Pd-Au piece when being used in combination (as reference) that performance can not show a candle to uses Pd-Au fashion (seeing embodiment 8).As another reference, (Pd: the Au weight ratio is 0.85: 1.0,140g/ft to have tested the system of only using Pd-Au 3Heap(ed) capacity).The CO emission of finding this system is 0.398g/km.
The inventor tests discovery, after Pt base and the catalyst that contains the physical mixed of Pd-Au are worn out, and CO oxidation susceptibility variation.When these catalyst are subjected to high temperature for a long time, except well-known metal sintering phenomenon, also find to cause the another kind of mode of performance decline, promptly form active less ternary alloy three-partalloy (Pt-Pd-Au) by sintering and in these systems.Experimental data shows that comprising first supported catalyst of platiniferous and the inactivation of the engine exhaust catalysts of second supported catalyst that contains palladium-gold grain is because formation ternary alloy three-partalloy (Pt-Pd-Au) causes.
Fig. 3 B-3D shows three kinds of different structures of the base material 210 of engine exhaust catalysts, and its purpose of design is to suppress the aging effect of these catalyst and makes best performanceization.The structure of above-mentioned three kinds of base materials 210 is physically separated the formation that suppresses ternary alloy three-partalloy by keeping platinum with palladium-Jin.The vehicle CO emission data of some embodiment of said structure are shown in table 1-4.Can clearly be seen that, the catalyst based advantage of using with the Pd-Au catalyst combination of Pt is maintained that the possibility that long-time simultaneously aging back forms ternary alloy three-partalloy reduces (for multilayer system) greatly or eliminates (for the polylith system) fully.
For the three-decker of Fig. 3 B, the cerium oxide base material in the intermediate layer can further reduce the migration of Pt and suppress ternary alloy three-partalloy and form.Referring to Nagai etc., " Sintering inhibitionmechanism of platinum supported on ceria-based oxide and Pt-oxide-supportinteraction ", J.Catal., the 242nd volume, 103-109 page or leaf (2006).Contain the palladium intermediate layer and can when sintering, form other bianry alloy and the sintering process that slows down (because compare with elemental metals, alloy more is not easy to sintering).
The preparation method of embodiment 1-11 is as follows.
The loaded PdAu catalyst of preparation 1.7%Pd, 2.0%Au
Lanthanum is stablized aluminium oxide, and (578g, surface area are about 200m 2g -1) and the deionized water (＞18M Ω) of 2940mL add in the plastic beaker of 5L and in about 500rpm lower magnetic force stirring.Recording pH is 8.5, and recording temperature is 25 ℃.After 20 minutes, with progressively adding Pd (NO in 10 minutes 3) 2(14.8% aqueous solution of 67.8g).Recording pH is 4.3.Stir after 20 minutes, with 5 minutes adding second metal HAuCl 4(24g is dissolved in the deionized water of 50mL).PH is 4.0, and the temperature of metallic carrier slurries is 25 ℃.Metal-carrier pulp was stirred extra 30 minutes.In second container, with NaBH 4(29.4g) and NaOH (31.1g) add N 2H 4(35% aqueous solution of 142mL), and stir up to mixture change clarification.This mixture constitutes reductant solution.With two peristaltic pumps metal-carrier pulp and reducing agent mixture are merged continuously.Mix in order to form turbulent flow, use the breeches joint that is connected to the Vigreux post to merge this two streams.The product that to leave mixing chamber (being the Vigreux post) pumps into less intermediate receptacle of volume and continuous stirring.Product in the intermediate receptacle is continuously pumped into bigger container (that is the beaker of 5L) storage and continuous stirring.。Whole interpolation/mixed process continues about 30 minutes.In bigger container, stir extra 1 hour of the product slurries of gained.Final pH is 11.0, and temperature is 25 ℃.Be that the Buchner funnel of double-deck filter paper of 3 μ m is with the product dope filtration with vacuum technique by hole is housed then.Being divided into roughly the same several parts with the deionized water of about 20L then washs filter cake.Then, with the filter cake after the washing 110 ℃ down dry, grind to form fine powder with mortar and pestle, calcine down at 500 ℃ then that (rate of heat addition was 8 ℃ of min in 2 hours -1).(1.7%Pd 2.0%Au) is used to prepare embodiment 3,5,6,7,9,10 and 11 with this loaded PdAu catalyst fines.
Preparation 2.8%Pt, 1.4%Pd supported catalyst
The La that adds 1940g in the deionized water of 10L stablizes aluminium oxide, and (the BET surface area is about 200m 2g -1), at room temperature stirred then 30 minutes.Pt (the NO that in these slurries, adds 490.6g 3) 2Solution (12.23wt%Pt (NO 3) 2), at room temperature stirred then 60 minutes.Use 12 minutes then acrylic acid (750mL, 99% purity) is added this system, and with gained mixture continuous stirring 2 hours at room temperature.From liquid, separate the loaded Pt catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours, obtain the 3%Pt material.
In the deionized water of 9.25L, add the above-mentioned 3%Pt material of 1822g, at room temperature stirred then 20 minutes.Pd (the NO that in these slurries, adds 194.4g 3) 2Solution (14.28wt%Pd (NO 3) 2), at room temperature stirred then 60 minutes.Added aqueous ascorbic acid (930g is in the 4.5L deionized water) with 25 minutes then, stirred then 60 minutes.From liquid, separate the loaded PtPd catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours, obtain 3%Pt, 1.5%Pd material.By the alumina support that adds blank La doping this material is diluted to 2.8%Pt, 1.4%Pd, and the mixture after will diluting is used to prepare embodiment 1,2,8,9 and 11.
Preparation 2.0%Pt, 1.0%Pd supported catalyst
The La that adds 2000g in the deionized water of 10L stablizes aluminium oxide, and (the BET surface area is about 200m 2g -1), at room temperature stirred then 30 minutes.Pt (the NO that in these slurries, adds 327.1g 3) 2Solution (12.23wt%Pt (NO 3) 2), at room temperature stirred then 60 minutes.Use 12 minutes then acrylic acid (500mL, 99% purity) is added this system, and with gained mixture continuous stirring 2 hours at room temperature.From liquid, separate the loaded Pt catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours, obtain the 2%Pt material.
In the deionized water of 9.5L, add the above-mentioned 2%Pt material of 1900g, at room temperature stirred then 20 minutes.Pd (the NO that in these slurries, adds 135.3g 3) 2Solution (14.28wt%Pd (NO 3) 2), at room temperature stirred then 60 minutes.Added aqueous ascorbic acid (647.2g is in the 3.5L deionized water) with 25 minutes then, stirred then 60 minutes.From liquid, separate the loaded PtPd catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours, obtain 2%Pt, 1%Pd material.This material is used to prepare embodiment 4,5 and 7.
Preparation 3.0%Pt, 0.75%Pd supported catalyst
The La that adds 2000g in the deionized water of 10L stablizes aluminium oxide, and (the BET surface area is about 200m 2g -1), at room temperature stirred then 30 minutes.Pt (the NO that in these slurries, adds 654.2g 3) 2Solution (12.23wt%Pt (NO 3) 2), at room temperature stirred then 60 minutes.Use 12 minutes then acrylic acid (500mL, 99% purity) is added this system, and with gained mixture continuous stirring 2 hours at room temperature.From liquid, separate the loaded Pt catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours, obtain the 4%Pt material.
In the deionized water of 9.5L, add the above-mentioned 4%Pt material of 3800g, at room temperature stirred then 20 minutes.Pd (the NO that in these slurries, adds 135.3g 3) 2Solution (14.28wt%Pd (NO 3) 2), at room temperature stirred then 60 minutes.Added aqueous ascorbic acid (647.2g is in the 3.5L deionized water) with 25 minutes then, stirred then 60 minutes.From liquid, separate the loaded PtPd catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours, obtain 4%Pt, 1%Pd material.By the alumina support that adds blank La doping this material is diluted to 3.0%Pt, 0.75%Pd, and the mixture after will diluting is used to prepare embodiment 3 and 6.
Preparation 3.0%Pt, 2.0%Bi supported catalyst
The La that adds 2000g in the deionized water of 10L stablizes aluminium oxide, and (the BET surface area is about 200m 2g -1), at room temperature stirred then 30 minutes.Pt (the NO that in these slurries, adds 436.1g 3) 2Solution (13.76wt%Pt (NO 3) 2), at room temperature stirred then 60 minutes.Use 12 minutes then acrylic acid (750mL, 99% purity) is added this system, and with gained mixture continuous stirring 2 hours at room temperature.From liquid, separate the loaded Pt catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours.
Stablize adding bismuth acetate solution (the 59.1g bismuth acetate is in 1.4L deionized water and 0.25L glacial acetic acid) in the loaded 3%Pt catalyst of aluminium oxide to the La of the 1600g that as above prepares.With gained paste mechanical mixture 10 minutes at room temperature, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under calcining 2 hours in air, finally obtain being used to prepare loaded 3.0%Pt, the 2.0%Bi catalyst of embodiment 10.
Preparation 3.0%Pd supported catalyst
(based on cerium oxide-zirconia, the BET surface area is about 90m to the rare earth oxide carrier of adding 1000g in the deionized water of 5L 2g -1), at room temperature stirred then 20 minutes.Pd (the NO that in these slurries, adds 211.8g 3) 2Solution (14.28wt%Pd (NO 3) 2), at room temperature stirred then 60 minutes.Added aqueous ascorbic acid (1013g is in the 5L deionized water) with 25 minutes then, stirred then 60 minutes.From liquid, separate the loaded PtPd catalyst solid of aluminium oxide that La mixes by filtering, 120 ℃ dry 2 hours down, grind to form fine powder and (rate of heat addition is 8 ℃ of min 500 ℃ temperature -1) under in air the calcining 2 hours, obtain loaded 3%Pd material.This material is used to prepare embodiment 11.
Embodiment 1. three-deckers: ground floor PtPd (57.5g/ft 3 ), second layer β zeolite, the 3rd layer PtPd (57.5g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.8%Pt 1.4%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 2.5 inches), 120 ℃ of dry down and calcinings under 500 ℃, obtain the ground floor of the single piece of material of multiple coating, the heap(ed) capacity of PtPd is about 57.5g/ft 3
Then, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, the β zeolite is made the coating slurries.According to methods known in the art, zeolite coating slurries are coated on the cordierite single piece of material (having the PtPd ground floor), 120 ℃ of dry down and calcinings under 500 ℃, obtain the second layer of the single piece of material of multiple coating.Zeolite mixture accounts for about 20% of the total heap(ed) capacity of coating.
Then, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.8%Pt 1.4%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated on the cordierite single piece of material (having the PtPd ground floor and the zeolite second layer), 120 ℃ down dry and 500 ℃ of calcinings down, obtain the 3rd layer of single piece of material of multiple coating, the heap(ed) capacity of PtPd is about 57.5g/ft 3
According to the single piece of material encapsulation of methods known in the art, and adopt certified means of testing that light diesel vehicle is tested as mentioned above with multiple coating.
Embodiment 2. three-deckers: ground floor PtPd (57.5g/ft 3 ), second layer zeolite mixture, the 3rd Layer PtPd (57.5g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.8%Pt 1.4%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 2.5 inches), 120 ℃ of dry down and calcinings under 500 ℃, obtain the ground floor of the single piece of material of multiple coating, the heap(ed) capacity of PtPd is about 57.5g/ft 3
Then, equiponderant β zeolite and ZSM-5 zeolite are mixed, and by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, be made into the coating slurries.According to methods known in the art, zeolite coating slurries are coated on the cordierite single piece of material (having the PtPd ground floor), 120 ℃ of dry down and calcinings under 500 ℃, obtain the second layer of the single piece of material of multiple coating.Zeolite mixture accounts for about 20% of the total heap(ed) capacity of coating.
Then, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.8%Pt 1.4%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated on the cordierite single piece of material (having the PtPd ground floor and the zeolite second layer), 120 ℃ down dry and 500 ℃ of calcinings down, obtain the 3rd layer of single piece of material of multiple coating, the heap(ed) capacity of PtPd is about 57.5g/ft 3
According to the single piece of material encapsulation of methods known in the art, and adopt certified means of testing that light diesel vehicle is tested as mentioned above with multiple coating.
Embodiment 3. three-deckers: ground floor PdAu (65g/ft 3 ), second layer zeolite mixture, the 3rd Layer PtPd (65g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (1.7%Pt 2.0%Pd) makes the coating slurries with the loaded PdAu catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 2.5 inches), 120 ℃ of dry down and calcinings under 500 ℃, obtain the ground floor of the single piece of material of multiple coating, the heap(ed) capacity of PdAu is about 65g/ft 3
Then, equiponderant β zeolite and ZSM-5 zeolite are mixed, and by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, be made into the coating slurries.According to methods known in the art, zeolite coating slurries are coated on the cordierite single piece of material (having the PdAu ground floor), 120 ℃ of dry down and calcinings under 500 ℃, obtain the second layer of the single piece of material of multiple coating.Zeolite mixture accounts for about 20% of the total heap(ed) capacity of coating.
Then, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (3.0%Pt 0.75%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated on the cordierite single piece of material (having the PdAu ground floor and the zeolite second layer), 120 ℃ down dry and 500 ℃ of calcinings down, obtain the 3rd layer of single piece of material of multiple coating, the heap(ed) capacity of PtPd is about 65g/ft 3
According to the single piece of material encapsulation of methods known in the art, and adopt certified means of testing that light diesel vehicle is tested as mentioned above with multiple coating.
Embodiment 4. polylith structures: Pt/Pd (120g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.0%Pt 1.0%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in the preceding piece and (every: Corning of back piece of circular cordierite single piece of material, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ of dry down and calcinings under 500 ℃, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal (Pt+Pd) is 120g/ft 3According to methods known in the art the single piece of material that applies is encapsulated, and adopt certified means of testing that light diesel vehicle is tested as mentioned above.
Embodiment 5. polylith structures: preceding Pt/Pd (120g/ft 3 ), back piece PdAu (175g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.0%Pt 1.0%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 120g/ft 3PtPd.This is as the preceding piece of two block systems.
In addition, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (1.7%Pd 2.0%Au) makes the coating slurries with the loaded PdAu catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 175g/ft 3PdAu.This is as back of two block systems.
Then, with the PtPd single piece of material (preceding) that applies with the PdAu single piece of material (back piece) of coating encapsulates so that preceding engine the most close (thereby at first being exposed to exhaust), and adopt certified means of testing that light diesel vehicle is tested as mentioned above according to methods known in the art.
Embodiment 6. polylith structures: preceding Pt/Pd (130g/ft 3 ), back piece PdAu (130g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (3.0%Pt 0.75%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 130g/ft 3PtPd.This is as the preceding piece of two block systems.
In addition, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (1.7%Pd 2.0%Au) makes the coating slurries with the loaded PdAu catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 130g/ft 3PdAu.This is as back of two block systems.
Then, with the PtPd single piece of material (preceding) that applies with the PdAu single piece of material (back piece) of coating encapsulates so that preceding engine the most close (thereby at first being exposed to exhaust), and adopt certified means of testing that light diesel vehicle is tested as mentioned above according to methods known in the art.
Embodiment 7. polylith structures: preceding Pt/Pd (150g/ft 3 ), back piece PdAu (130g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.0%Pt 1.0%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.This adds cerium oxide-zirconia to these coating slurries, so that cerium oxide-silica accounts for about 28wt%.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 150g/ft 3PtPd.This is as the preceding piece of two block systems.
In addition, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (1.7%Pd 2.0%Au) makes the coating slurries with the loaded PdAu catalyst fines of as above preparation.This adds cerium oxide-zirconia to these coating slurries, so that cerium oxide-silica accounts for about 28wt%.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 130g/ft 3PdAu.This is as back of two block systems.
Then, with the PtPd single piece of material (preceding) that applies with the PdAu single piece of material (back piece) of coating encapsulates so that preceding engine the most close (thereby at first being exposed to exhaust), and adopt certified means of testing that light diesel vehicle is tested as mentioned above according to methods known in the art.
Embodiment 8. polylith structures: preceding Pt/Pd (170g/ft 3 ), the blank single piece of material of back piece
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.8%Pt 1.4%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 170g/ft 3PtPd.This is as the preceding piece of two block systems.In addition, with piece after cordierite single piece of material (Corning, 400cpsi, 5.66 inches * 1.25 inches) conduct of the equal blank of size.Then, according to methods known in the art with the single piece of material that applies and the encapsulation of blank single piece of material so that preceding engine the most close (thereby at first being exposed to exhaust), and adopt certified means of testing that light diesel vehicle is tested as mentioned above.
Embodiment 9. polylith structures: preceding Pt/Pd (170g/ft 3 ), back piece PdAu (146g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.8%Pt 1.4%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 170g/ft 3PtPd.This is as the preceding piece of two block systems.
In addition, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (1.7%Pd 2.0%Au) makes the coating slurries with the loaded PdAu catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 146g/ft 3PdAu.This is as back of two block systems.
Then, with the PtPd single piece of material (preceding) that applies with the PdAu single piece of material (back piece) of coating encapsulates so that preceding engine the most close (thereby at first being exposed to exhaust), and adopt certified means of testing that light diesel vehicle is tested as mentioned above according to methods known in the art.
Embodiment 10. polylith structures: preceding PtBi (120g/ft 3 ), back piece PdAu (146g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (3.0%Pt 2.0%Bi) makes the coating slurries with the loaded PtBi catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 120g/ft 3Pt.This is as the preceding piece of two block systems.
In addition, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (1.7%Pd 2.0%Au) makes the coating slurries with the loaded PdAu catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated in circular cordierite single piece of material (Corning, 400cpsi, 5.66 inch * 1.25 inches), 120 ℃ down dry and 500 ℃ of calcinings down, finally obtain the single piece of material that applies, the heap(ed) capacity of its noble metal is 146g/ft 3PdAu.This is as back of two block systems.
Then, with the PtBi single piece of material (preceding) that applies with the PdAu single piece of material (back piece) of coating encapsulates so that preceding engine the most close (thereby at first being exposed to exhaust), and adopt certified means of testing that light diesel vehicle is tested as mentioned above according to methods known in the art.
Embodiment 11. sandwich constructions: ground floor PdAu (73g/ft 3 ), second layer Pd (30g/ft 3 ), The 3rd layer of PtPd (85g/ft 3 )
By adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (1.7%Pt 2.0%Au) makes the coating slurries with the loaded PdAu catalyst fines of as above preparation.According to methods known in the art, the coating slurries are coated on the circular cordierite single piece of material (Corning, 400cpsi, 5.66 inches * 2.5 inches), 120 ℃ of dry down and calcinings under 500 ℃, obtain the ground floor of the single piece of material of multiple coating.
Then, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, the loaded Pd catalyst (3.0%Pd) of as above preparation is made the coating slurries.According to methods known in the art, Pd coating slurries are coated on the cordierite single piece of material (having the PdAu ground floor) of multiple coating, 120 ℃ of dry down and calcinings under 500 ℃, obtain the second layer of the single piece of material of multiple coating, the Pd heap(ed) capacity is about 30g/ft 3
Then, by adding deionized water, wearing into suitable particle size (d 50Be generally 3-7 μ m) and regulate pH so that coating has the viscosity that is suitable for applying, (2.8%Pt 1.4%Pd) makes the coating slurries with the loaded PtPd catalyst fines of as above preparation.According to methods known in the art, PtPd coating slurries are coated on the cordierite single piece of material (having the PdAu ground floor and the Pd second layer) of multiple coating, 120 ℃ down dry and 500 ℃ of calcinings down, obtain the 3rd layer of single piece of material of multiple coating, the heap(ed) capacity of PtPd is about 85g/ft 3
The precious metal loadings of the single piece of material that the multilayer of gained (being three layers herein) applies is: ground floor PdAu is about 73g/ft 3, second layer Pd is 30g/ft 3, the 3rd layer of PtPd is 85g/ft 3According to the single piece of material encapsulation of methods known in the art, and adopt certified means of testing that light diesel vehicle is tested as mentioned above with multiple coating.
Although described the specific embodiment of the present invention above, it will be appreciated by those skilled in the art that the present invention can take various forms and embodiment within the scope of the appended claims.

Claims (20)

1. emission control catalyst that is used to handle engine exhaust, comprise the first catalytic activity district and the second catalytic activity district, the wherein said first catalytic activity district is oriented to make it to contact described engine exhaust before the described second catalytic activity district, and the wherein said first catalytic activity district comprises first supported catalyst that comprises the platinum metal particle that is supported on the oxide carrier, and the described second catalytic activity district comprises second supported catalyst of being made up of the palladium-Jin metallic particles that is supported on the oxide carrier basically.
2. emission control catalyst as claimed in claim 1 also comprises the base material with honeycomb of being with gas flow channel, and wherein said first supported catalyst and described second supported catalyst are applied on the wall of described gas flow channel.
3. emission control catalyst as claimed in claim 2, wherein a plurality of layers are applied on the described wall of described gas flow channel, and the bottom that is located immediately on the described wall of described gas flow channel comprises described second supported catalyst, and the top layer that is oriented to directly to contact with described engine exhaust comprises described first supported catalyst.
4. emission control catalyst as claimed in claim 3, wherein said first supported catalyst comprises platinum-palladium metal particle.
5. emission control catalyst as claimed in claim 3, wherein said top layer also comprises zeolite.
6. emission control catalyst as claimed in claim 3, wherein said a plurality of layers also comprise the intermediate layer between described bottom and described top layer.
7. emission control catalyst as claimed in claim 6, wherein said intermediate layer comprises zeolite.
8. emission control catalyst as claimed in claim 1, also comprise base material with upstream and catchment, described upstream is oriented to make it to contact with described engine exhaust before described catchment, wherein said first supported catalyst is applied to the described upstream of described base material, and described second supported catalyst is applied to the described catchment of described base material.
9. emission control catalyst as claimed in claim 1, also comprise upstream single piece of material and downstream single piece of material, described upstream single piece of material is oriented to make it to contact with described engine exhaust before the single piece of material of described downstream, wherein said first supported catalyst is applied on the single piece of material of described upstream, and described second supported catalyst is applied on the single piece of material of described downstream.
10. emission control catalyst that is used to handle engine exhaust, described catalyst comprises base material, described base material has the first paint metal particle that comprises platinum and comprises basically second coating of the metallic particles of being made up of palladium and gold, and wherein said first coating is oriented to make it to contact with described engine exhaust before described second coating.
11. as the emission control catalyst of claim 10, wherein said first coating also comprises zeolite.
12. the emission control catalyst as claim 10 also comprises the 3rd coating that contains zeolite.
13. emission control catalyst as claim 10, wherein said base material has the honeycomb of band gas flow channel, layered coating is applied on the wall of described gas flow channel, and wherein the bottom that directly contacts with the described wall of described gas flow channel comprises described second coating, is positioned to comprise described first coating with top layer that described engine exhaust directly contacts.
14. as the emission control catalyst of claim 13, wherein said multilayer comprises the intermediate layer between described bottom and described top layer, and described intermediate layer comprises the 3rd coating that contains zeolite.
15. emission control catalyst as claim 10, wherein said base material has upstream and catchment, described upstream is oriented to make it to contact with described engine exhaust before described catchment, and wherein said first coating is applied to the described upstream of described base material, and described second coating is applied to the described catchment of described base material.
16. emission control catalyst as claim 10, wherein said base material has upstream single piece of material and downstream single piece of material, and wherein said first coating is applied on the described upstream single piece of material of described base material, and described second coating is applied on the described downstream single piece of material of described base material.
17. emission control catalyst, comprise first catalyst and second catalyst, described first catalyst comprises the platinum metal particle, described second catalyst comprises and contains palladium-Jin metallic particles and do not comprise platinum-palladium-Jin metallic particles, and described emission control catalyst has each the district that separates physically that is used for described first catalyst and described second catalyst.
18., also comprise physically separated being used for the district of described first catalyst and being used for buffering area between the district of described second catalyst as the emission of claim 17 control catalyst.
19. as the emission control catalyst of claim 17, wherein said first catalyst comprises Pt: the Pd weight ratio is 2: 1-4: platinum-palladium catalyst of 1, described second catalyst has 0.5: 1-2: 1 Pd: the Au weight ratio.
20. the emission control catalyst as claim 19 comprises that also containing weight ratio is about 1: the 1 β zeolite and the zeolite mixture of ZSM-5 zeolite.
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